Method and apparatus for treating hydrocarbons



July 5, 1960 w. o. wEBBER METHOD AND APPARATUS FOR TREATING HYDROCARBONS Filed Deo. 6, 1957 2 Sheets-Sheet 1 Zehn-...Om

mm mm SICE@ Nv m o SCE 32mm July 5, 1960 w. o. wEBBER 2,944,010

METHOD AND APPARATUS FOR TREATING HYDRQCRBONS Filed Dec. 6, 1957 2 Sheets-Sheet 2 INVENTOR.

WILLIAM O. WEBBER,

NIETHOD AND APPARATUS FOR TREATIN G HYDRCARBONS William O. Webber, Baytown, Tex., assignor, by mesne assignments, to Esso Research and Engineering Com'- pany, Elizabeth, NJ., a corporation of Delaware Filed Dec. 6, 1957, Ser. No. 701,088

16 Claims. (Cl. 208-177) Y The present invention is directed to a method and apparatus for admixing and separating immiscible liquids, More particularly, the invention is directed to a method for treating a hydrocarbon with a liquid immiscible with the hydrocarbon.l In its more specic aspects the invention is concerned with method and apparatus for removing deleterious substances from hydrocarbons.

The present invention may be brieflydescribed as a method for admixing and separating inmmiscible liquids or for treating immiscible liquids which comprises owing a first liquid through a restricted zone. Introduced into the iirst liquid as it ows through the vena contracta of the restricted zone is a second liquid immiscible in the iirst liquid which is introduced at a plurality of circumferentially spaced apart points to form a mixture of the liquids. The mixture is then owed through a horizontal elongated zone and the mixture is coagulated as it flows through the elongated zone. Thereafter, the coagulated mixture is settled into the iirst and second liquids.

The invention also includes apparatus for admiring and separating immiscible liquids or for treating one liquid with another immiscible liquid. The apparatus comprises, in combination, a restriction means which suitably may be uid pressure operated valve having an inlet and an outlet. Means are provided for introducing a rst iluid into the inlet of the tiuid pressure operated valve and a tubular ring provided with a plurality of circumferentially spaced apart connections uidly communicates with the vena contracta of the valve. Means are provided for introducing into the ring a second fluid immiscible in the yfirst iluid. A horizontally arranged tubular member is connected by its first end to the outlet of the valve and spaced apart oriiices are arranged in the horizontal tubular member. A settling vessel connects to the second end of the horizontal tubular member for separation of the fluids.

By vena contrasta is meant, in a hydraulic sense, any of the contracted parts of minimum size of a jet of uid discharging from an on'ce or an aperture. For example, a uid pressure diaphragm operated valve has a vena contracta below the seat of the Valve.

One of the imrniscible liquids may suitably be a liquid hydrocarbon boiling in the range from about 80 up to about 750 F. As exemplary of such liquid hydrocarbons may be mentioned the pentanes, the hydrocarbons in the gasoline and kerosene boiling range, and the gas oil hydrocarbons. The hydrocarbon may be a pure hydrocarbon or a mixture of hydrocarbons.

'Ihe hydrocarbon may be treated for removal of impurities, such as hydrogen suliide, mercaptans and other impurities which are normally removed in the refiningof hydrocarbons.

The liquid immiscible in the hydrocarbon or in the irst liquid may suitably be a liquid treating reagent, such as a sodium hydroxide or caustic solution or may be an alkaline hypochlorite solution, such as sodium hypochlorite. Suitably, the liquid may be Water or an aqueous or an alcoholic solution which may be used to 'ltent patented July 5, 1960 treat or wash hydrocarbons. The immiscible liquid may be an acid, such as a sulfuric acid, and the like, or may be any of the numerous liquid treating reagents used in a modern petroleum renery.

The present invention will be further illustrated by reference to the `drawing in which:

Fig. 1 is a tiow diagram of a preferred mode; and

Fig. 2 is an enlarged partial cut-away View in perspective showing the ring and the valve employed to form the mixture.

Referring now to the drawing in which identical numerals will be employed to designate identical parts, numeral 11 designates a feed line by way of which a feed hydrocarbon, such as a pentane fraction or a stable naphtha may be introduced into the system from a source, not shown. The feed hydrocarbon, by Way of line 11, is introduced into the inlet of a iluid pressure operated valve, such as a diaphragm valve 12, which is provided with a diaphragm 13 and a differential pressure control means 14 which operates on differential pressure between the pressure taps 15 and 16. The feed hydrocarbon ows into the inlet of valve 12 and is admixed with an immiscible liquid' or treating solution, in this instance caustic solution introduced by line 17 from a source which Will be described further. By virtue of introducing the caustic solution into the vena contracta of the valve 12, an eicient mixing of the feed hydrocarbon with the caustic solution is effected. The mixture then tlows from the outlet of the valve 12 by Way of line 1S through rst and second orifices 19 and 2t) and thence by way of line 21 into a settling zone 22. The partially treated naphth-a iiows from settling zone 22, which is of suicient size and capacity to make a separation between the hydrocarbon and the caustic solution, by way of line 23, for further treatment as will be described.' The caustic solution separated in settler 22 is withdrawn by way of line 24 and flows through a liquid level control valve 25 to a pump 26 which pumps the caustic solution through line 27 into branch line 28, controlled by valve 29, into line 17. It is to be noted that line 27 is provided With a valve 34) for discard of a portion of the used caustic solution and that line 17 is provided with a valve 31 for introducing fresh or makeup caustic solution. The circulating caustic solution may have a Baum gravity of about 18 Which suitably may range from about 15 to about 20 Baume. The purpose of this caustic treatment is to remove hydrogen sulde and low molecular weight mercaptans from the feed hydrocarbon The treated hydrocarbon in line 23 from which hydrogen sulfide has been substantially removed, ilows by way of line Z3 into a second diaphragm valve 32 which may be identical to diaphragm Valve 12. In this particular instance, an alkaline hypochlorite solution, such as sodium hypochlorite, is introduced lby line 33 into the vena contracta of the Valve 32, the valve 32 being provided with a diaphragm 34 and a diierential pressure control means 35 operated from the pressure taps 36 and 37.

The outlet from valve 32 is connected to line 38, and the mixture of hypochlorite solution and treated naphtha flows through line 3d and through oriiices 39 and 40 and thence by way of line 41 into a settling zone 42, which is similar in size and capacity to settler 22. The treated and settled naphtha is Withdrawn from settler 42 by Way of line 43. The used hypochlorite solution is Withdrawn from settler 42 by way of line 44, controlled by a liquid level control valve 45 and is pumped by Way of pump 46 into line 47 and thence by branch line 4S, controlled by valve 49, into line 33. It is to be noted .that line 47 is provided with a valve 50 for discard of a portion of the used hypochlorite solution and line 33 is provided with a valve 51 for introduction of fresh or regenerated hypochlorite solution.

'lhe circulating hypochlorite solution may have an alkalinity in the range from vabout .100 to about V175 `grams/liter and may have an available chlorine content in the range from about 0.1 to about 100 grams/liter.

' .xlyfof .the Aadmixing and separating device of the present invention, .the ltreated and settled foilfi's treated ei`n`ciently with Aa minimum amount .and consumption of the treating reagents.

iRetemingznow to Fig. 2, the treated-oil from ithe settler 22 tlows Vby way of line .23 vinto the valve 32, which is provided vwith a-diap'hragm l34. Connected into the vena conn-'acta 55 .of .the valve .32 is a ring 56, provided with a plurality of circumferentially arranged fluid communication connections 57, which may be four in number. TheY l ring 56 .fluidly communicates with line 33 vhyway of which fthe ,hypochlorite solution is introduced into the ring 5:6 :and .thence to the vena .contrasta S5. It is to .be noted that thel line 23 connects .into the inletSS of the ualvezand that the outlet 59 .connects 'mto .the line ,38 containing the orifices Y3.9 'and 40. AAs shown 'clearly in the -cut-away portions of the valve `321the valve 32 is provided witha fseat 60 and 'the duid communication means 5.7 .are connected by means of ports 61 into the vena :contrasta v5,5 'of .the valve 32.

rBy virtue of apparatus .and method as described herein effrcient mixing, settling, coagulating, and treatment are obtained between vhydrocarbons and immiscible treating reagents. `Inthe practice of the .present invention a large volume of-o'il'is jetted through an vorifice or restriction means .and 'a Etreating solution, suchas has been illustrated, is intro duced'iaround the vena contracta vwhere the oil flow necks down Aandthus lthe'tre'ating solution is educted into the fast ii'owingioil. The valve with the ring immediately downstream ofthe valve plug, rby means of which the ymixing Vis obtainedgprovides for etiicient and rapid mixing of the'hydrocarbon and Vtreating reagent. By virtue of employing eductive mixing, a smaller and more uniform size Vfofdropletis formed than otherwise. In'many mix- Ving-devices a wide range of droplets may occur and a settlerwhich follows lmust be properly sized yto provide theneeess'ary time-for settling of the small droplets, which may 'be 'as much as ten times the time required to settle the larger droplets. In the present invention, the small droplets Aare rmade to coagulate -with other small droplets or V'with larger droplets, and the settling is made eiicient `and-rapid. This'is accomplished inthe present invention Iproviding Vtwo orices in the lines 38 and 18 to cause coagulation. As examples, the iirst orince such vas 39 may have a diameter of about 1.29" and provide about four pounds pressure drop, while Vthe second orice may be somewhat larger, about 1.47" in diameter and provide about a two pound pressure drop. The pressure drop through the rst or'ice may range from about 2 to about pounds While the pressure drop through the second ori'ce may range from about 1A to about 4 pounds, the orifices Abeing Asuitably sized to -obtain the desired Vpressure drop at the prevailing ow rates. These coagulative orifices increase the efficiency by coagulating the droplets such that when thecoagulated mixture-is lintroduced into the settling zone the settling into the Vphases of the mixture is more rapid and eicient than heretofore.

' 'In employing the present invention where hydrocarbons containingmercaptans are treated to convert sour `mercaptans to disulfides with Ya strong hypochloritesolution, the sweetening reaction is quite rapid. However, along with the sweetening reaction Vis aparallel reaction wherein the 'strong available chlorine in the Vtreating solution chlorinates some of the hydrocarbonsl present. The chlorination reaction is very rapid and may consume 'about 75 percent Yof the available chlorine, making it necessary Ysometimes to usek vabout four times as .much chlorine v.as

that theoretically Yrequired to convert mercaptans to disuldes. These reactions occur because of nthelarge sur- Iface ioffcontact Lbetween aqueous and oil phases, this 2,944,010 r e f surface being greater when the size of the aqueous droplets is small. By employing the present invention in .which a restriction means, such as a valve of the nature described, is followed with a coagulative orice plate or plates, the droplets are enlarged, the surface reduced, and the reaction is eiectively stopped. This reduces the consumption of chlorine and increases the efficiency of the hypochlorite treating process, thereby .reducing .the `cost of operationV and eliminating 'chlorinated hydrocarbons from the inished product.

As an example of the practice of the ipresent invention, in a commercial operation, pentanes Ywere 'being :treated with an alkaline Ihypoclilorite solution.` lBy employing the present invention, thechlorine consumption was reduced about 50 percent based on the measured reduction of strong hypochlorite solution `makeup fromabout 1 gallon per minute to about 0.5 gallon per minute.V In short, the present invention is quite eiective and useful and advantageous over Ythe prior art in that eflicientmixing and coagulation means .and methods 'areprovided Theznature and objects of the present vinvention having been .completely vdescribed and-illustrated, what I wishto claim as new and useful and secure by Letters Patentis:

l. A method for admixing and separating imrniscible liquids which .comprises .owing a first liquid Ahydrocarbon through a restricted zone, Yintroducing .into .said first liquid hydrocarbon Y*as it flows through the avena con- -tracta .of Ysaidzone .a second liquid .treating agent immis- .cibleinathe rst `liquid hydrocarbon Vat a plurality-of crcumferentially spacedapart points to form a mixture .of

Y small and uniform size droplets Yof .said liqufids,

the mixture through :an elongated zone, :coagulating the mixture 'as it flows vthrough said elongated zone, .and then settling the .coagulatedamixture into .said irst and .second liquids.

2. A method for admixing andseparating immiscible liquids which comprises Vflowinga iirst liquid hydrocarbon through a restricted zone, Yintroducing into .said nrst liquid hydrocarbon vas .it ows through .the vena contracte of said zone a second liquid treating agentimmiscible'in the iirst liquid hydrocarbon at a plurality of circumferen- -tially-spaced vapartpoints torform a mixture of small and uniform size droplets of said liquids, owing the mixture through a .horizontal elongated zone, coagulating .the mixture at spaced apart ,points as it liows .through-said elongated zone, and then settling the Ycoagulated mixture into said lirst and vsecond liquids.

3.A method for admixing and separating irnmiscible liquids which comprises flowing a Airst liquid hydrocarbon through a restricted zone, introducinginto saidiirst liquid hydrocarbon as it ows through the vena contracta of said zone la second liquid treating agent immisciblejn the -lirst liquid hydrocarbon at a plurality of circumferentially spaced apart points to form a mixture of small and :uniform size droplets of said liquids, flowing Vthe mixture through a horizontal elongated zone, coagulating .the mixture at spaced apart points by progressively vdecreasing the pressure drop across restricted areas .in said elongated zone as the 'mixture flows through Asaid elon- :gated zone, and then Vsettlingthe icoagulated mixture 'into said first and secondliquids.

4. A method for .treating a liquid hydrocarbon which comprises flowing .said liquid hydrocarbon through arestricted zone, introducing into Ysaid liquid hydrocarbon as it lilows through the vena contracta ot said zone a liquid treating agent immiscible in the liquid hydrocarbon at a plurality of circumfereutially spaced apart points'to Yform a mixture ofsmall and uniform size droplets vof said liquid hydrocarbon and introduced liquid, flowing the mixture through an elongated zone, coagulating thernixture as it llows through said elongated zone, and then settling 'the coagulated mixture into saidliquid hydrocarbon andintroducedliquid.

Y5. A method for treating hydrocarbons which com'- prises ll'owing va liquid' hyrocarbon 'boiling up to Vabout 750 F. through a restricted zone, introducing into said liquid hydrocarbon as it iiows through the vena contracta of said zone an aqueous alkaline hypochlorite solution lat a plurality of circumferentially spaced -apart points to form a mixture of small and uniform size droplets of said hydrocarbon and solution, fowing the mixture through la horizontal elongated zone, coagulating the mixture as it ows through said elongated zone, and then settling the coagulated mixture into a treated hydrocarbon phase and a solution phase.

6. A method in accordance with claim 5 in which the liquid hydrocarbon is a pentane.

7. A method in laccordance with claim 5 in which the liquid hydrocarbon is naphtha.

8.A method in accordance with claim 5 in which the hypochlorite solution is sodium hypochlorite.

9. A method for treating a liquid hydrocarbon which comprises owing said liquid hydrocarbon through a restricted zone, introducing into said liquid hydrocarbon as it iiows through the vena contracta of said zone a liquid treating reagent immiscible in the liquid hydrocarbon at a plurality of circumferentially spaced apart points to form a mixture of small and uniform size droplets of said liquid hydrocarbon land treating reagent, owing the mixture through a horizontal elongated zone, coagulating the mixture as it ows through said elongated zone, and then settling the coagulating mixture into a treated hydrocarbons phase and a treating reagent phase.

10. A method in accordance with claim 9 in which the treating reagent is a sodium hydroxide solution.

11. A method in accordance with claim 9 in which the treating reagent is a sodium hypochlorite solution.

12. Apparatus for admixing and separating immiscible liquids which comprises, in combination, a restriction means having an inlet and an outlet, means for introducing `a -iirst fluid into the inlet of said restriction means, a tubular ring provided with -a plurality of circumferentially spaced apart connections uidly communicating with the vena contracta of said restriction means, means for introducing into said ring a second uid immiscible in the rst iiuid, a tubular member connected by its rst end to the outlet of said restriction means, spaced apart oriiices arranged in the tubular member, and Ia settling vessel connected to the second end of said tubular member.

1-3. Apparatus for admixing and separating immiscible liquids which comprises, in combination, a uid pressure operated valve having an yinlet and an outlet, means for introducing a first uid into the inlet of said valve, a tubular ring provided with a plurality of circumferentially spaced apart connections fluidly communicating with the vena contracta of said valve, means for introducing into said ring a second uid immiscible :in the iirst iluid, a horizontally arranged tubular member connected by its first end to the outlet of said valve, spaced apart orifices arranged in the horizontal tubular member, and a settling vessel connected to the second end of said horizontal tubular member.

14. Apparatus for admixing and separating immiscible liquids which comprises, in combination, a uid pressure diaphragm operated valve having an inlet and an outlet, a pipe connected to said valve for introducing a first uid into the inlet of said valve, a tubular ring provided with a plurality of circumferentally spaced apart connections uidly communicating with the vena contracta of said valve, a pipe connected to said ring for introducing into said -ring a second fluid immiscible in the irst iluid, a horizontally arranged tubular member connected by its rst end to the outlet of said valve, spaced apart orifices arranged in the horizontal tubular member, and a settling vessel connected to the second end of said horizontal tubular member.

15. Apparatus lfor admixing and separating immiscible liquids which comprises, in combination, a uid pressure operated valve having an inlet and an outlet, the outlet of said valve forming a right angle with the inlet of said valve, a horizontal pipe connected to said inlet -for introducing a first fluid into said valve, Ia tubular ring provided with a plurality of circumferentially spaced apart connections uidly communicating with the vena contracta of said valve, -a pipe connected to said ring for introducing into said ring a second uid immiscible -in the rst uid, a horizontally arranged tubular member connected by its first end to the outlet of said valve, spaced apart orifices arranged in the horizontal tubular member, and a settling vessel connected to the second end of said horizontal tubular member.

16. A method Iin accordance with claim 4 in which the introduced liquid is reactable with a component of the liquid hydrocarbon.

References Cited in the le of this patent UNITED STATES PATENTS 2,057,918 Ridgway Oct. 20, 1936 2,331,518 Trier et a1 Oct. 12, 1943 2,361,150 Petroe Oct. 24, 1944 2,608,523 Waddell et al Aug. 26, 1952 2,679,470 Kress May 25, 1954 2,768,123 Trusty et al. Oct. 23, 1956 2,773,019 Waddell Dec. 4, 1956 2,775,542 Carver Dec. 25, 1956 2,775,543 Carver et al Dec. 25, 1956 2,820,700 Saxton Jan. 21, 1958 

1. A METHOD FOR ADMIXING AND SEPARATING IMMISCIBLE LIQUIDS WHICH COMPRISES FLOWING A FIRST LIQUID HYDROCARBON THROUGH A RESTRICTED ZONE, INTRODUCING INTO SAID FIRST LIQUID HYDROCARBON AS IT FLOWS THROUGH THE VENA CONTRACTA OF SAID ZONE A SECOND LIQUID TREATING AGENT IMMISCIBLE IN THE FIRST LIQUID HYDROCARBON AT A PLURALITY OF CIRCUMFERENTIALLY SPACED APART POINTS TO FORM A MIXTURE OF 